2 amino ethyl 33 dimethyl norcamphane



?Peiate el m s mu 33 email" NORCAMPHA E Peter 11.. .de Benneville; Philadelphia, Pa., assi abrio' '5 Rohm &-Haas Company, Philadelphia, 211., a corpora.-

" tion of Delaware N o Drawing. apflieaan ram 28,1955

l'This invention concerns amines oilthe structure i i chornm N .CH: R2

V -ration wherein s-formyl 'caniphane or-Fhomoisocamphenilanaldehydeis reacted 'With' -a' sec'ondary amine andthe resulting enamine is reduced. 'Reduction may be ipexamplfes .iwherein 5' fr az-pat fe en' in the .followingfillnstrative --Further detailsl Pa ti lsP I-W ii.:r:

formrl icampharie iihere 'is: added 4 i ,7

" hy m um'ff rm te,-.p pa e .byip s a o 11 parts ;.of dime V formic acid, "The resulting'mixtureis heated anagra .ylamin A as gas. i to 1 ,5 parts of i 7 "bath with evolution of 'carbon dioxide .1for'a1tota1 of This invention also deals with al vmethodlfor their'prepa accomplished with. formic acid at 80. to 100i" 0. or more 5 or with l'ify'drogenation in the presence of a hydrogenation catalyst. I

It I :The enamines have been previously prepared and-found and giving the reaction of 'aldehydes. a

a represent. alkyl or alkeriyl groups usually of not over I t 12 carbon atoms, cycloalkyl, aralkyl, and aryl groups 'when taken individually orwhen taken together 'R and R "form a saturated divalent alphatic chain of four to 'ffive atoms which with the nitrogen forms a, fiveto sixsided heterocycle as in morpholine, thiamorpholine; piperidine, pyrrolidine, trimethy1pyrro1idine,- N-methyb They may be represented as five hours. The reaction mixture is ftreated'withpotas sium carbonate and distilled, The(main,frati0n 1S taken W at 75 -76 C./ 1.7 mm. It amounts t'o-34par't's .and corresponds in composition to j 1 v W an on 15 611. on, om: i athfj .il f y bg T eader-111g wan hyde dipenten e', 'dim'ethyla'mine, and'fformic-iacid,

' to give a, tertiary amine of the sam empiricaliforn iula.

It distills at 140 1693 c./'s o;mm., meioxo. aldehyde I from B-pinene reacted' witHdimethylamine and Lformic 'acid gives atertiary amine iofthesame empirical com! a position which distills at 7'.l-&78 j C/1 f 'nP i "i? i There are reacted 40parts of f 8f ormyl camphane and 7 43p'arts of dibut-ylarhinefi'Thereactionimixtureisistirred 7 Q Thefcompound' 8 formylfcamphane, as is knowm can Y I to be unstable, readilyhydrolyzing in aqueous systems l heated on a Sffififil bath; .It is ta en n-i 1mm of heptaneiand lO'fparts of Raneyg nickel'isiadded. The mixture is; heated under hydrogen-mienautoclave at 130 C. for threehours a't 1750p. The" autoclave v is cooled and vented." The.?Teaction, mixture is 'filtered.

The filtrate is distilled. Atg125iE -l350 C./ 1.7 mm. a

' fractionof 35 parts of 'fairly pure -tertiary amine is obtained. It is dissolved. in "dilute hydrochloric acid.

, like. Typical of these chains are CH CH OCH CI-Ii+;,

R are individual groups, theyfmaybe methyl, ethyl, propyl, butyl, sec-butyl, isobutyl, amyl, hexyl, octyl,

r 45 piperazine, methylmorpholine, methylpiperidine, and the This solutionlis extracted with heptane. The acid Sony; tion is madebasic' with potassium hydroxide solution and ,extractedwith toluene The toluenelayer is dried over potassium"carbonateland distilled. I At 130- -.131" "C.-/ 1. 6 I mm. there is obtained a fraction of 23 parts of the def 1 sired tertiary amine z in has a: refractive index, fin i, of-1.4703.

' Example 3 dodecyl, allyl, crotyl, undecenyl, dodecenyl, -benzyl,',

' methylbenzyl, cyclohexyl, v butylphenyl, chlorophenyl, etc.

v The preferred groups are'alkyl radicals of notbver four carbon atoms and the above'specified divalent- The individual R groups may be the aliphaticIgroups.

- s amefor different. p w r 1 Reaction of 8-formyl camphane and'secondary'amine,

" maybe first effected between 25 9 'and 100 C; and the camphane, secondary amine; and formic acid may ,be

' dioxide-usually between 80?. andiIQOKC.

from 20 to 150 C. y' i t 1 methylcyclohexyl, phenyl,

Hydrogenation of the reaction product ofQS-formyl amphane and secondary amine inayibe accomplished at ;.tlie' temperature dictated by ,thecatalyst chosen. Thus with platinum or palladium re'ductionican be completed. I at"2'5 to 75 C.,=,While withaRaney-nickel.temperatures reaction product thereof then reduced. Again, 8-fo rmyl vrni x'ed and the mixture heated with evolutionof'carbonfi V -In the same wayf .and. .piperidine 26 '.;pa rts\..;fo1f.theaboveffl ipart fof "morpholinel. wThe rmltingFenamine is;reduced and;th

and'97" C. 'at 0.5 mm pressure;

30 parts of morpholine. Therreaction mixturejistreated I as above, being heated on asteam bath, extracted with a, close-cut petroleum naphtha, and. hydrogenated over Raneynickel- Thefiltered reaction mixture is then dis tilled. The. main fraction is {taken at 1025-104 C ./O .5

mm. It is a tertiary amine corresponding in composition to i f c M, i

' oHomoHiN. "o

.Hfll ,o-cn cmo, It has a refractive index of .4281 at 25 ere. aref-reactedi8 formyl camp product pur' ed b y distillation; the main amn on. of: the analogousfpiperidino compound being' takenbetw'efi 1 8 corrosion inhibitors for strong acids.

Reaction-of 42 parts of 8-formyl camphane and 30 parts of pyrrolidine followed by hydrogenation and 'distillation gives a main fraction of the pyrrolidino analogue coming over at 80 92{ C. 0.5 mm.

These amines are useful for forming salts with nitrophenols, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichloroacetic acid, penicillin, his(hydroxychlorophenyl)methane or sulfide, and the like. The amines are effective For example, the rate of attackof steel by dilute hydrochloric acid solutions can be reduced over 90% or more by the presence of a few tenths percent of one of the amines of this invention in the acid.

I claim:

1. A compound of the formula 7 CH i j R} H, 1 2 CH E CH CH: z Where R and R are taken from the class consisting of lower alkyl groupswhen taken individually. and when taken together saturated divalent aliphaticchains of four to five atoms which form a fiveto six-sided heterocyclic amine with the nitrogen. a

2; A compound of .the formula where' R and R are lower alkyl groups.

3. The compound v 4 4. The compound I CHCHzOH2N(C4HB)2 OH: CH\: (Ii-CH: on, 5. A compound of the formula (1H2 CHCH2CH2N A CH\ I 2 G OH3 CH CH3 Where A is a saturated divalent aliphatic chain of four to five atoms forming a five to six-sided heterocyclic amine with the nitrogen.

6. The compound 7 References Cited in the file of this patent UNITED STATES PATENTS De Benneville Dec. 18, 1951 OTHER REFERENCES 7 Huckel et a1.: Berichte, vol. B, pp. 959-963, 1937. 

1. A COMPOUND OF THE FORMULA
 6. THE COMPOUND 